双语化学辞典Chem Lexicon
研究生Graduate 聚合反应与高分子物理 Polymerisation & polymer physics

WLF 方程Williams–Landel–Ferry equation

\[\lg a_T = -\frac{C_1(T - T_\text{ref})}{C_2 + T - T_\text{ref}},\qquad C_1 \approx 17.44,\ C_2 \approx 51.6\ \mathrm K\ (T_\text{ref} = T_g)\]

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’ constants1, K

推导Derivation

  1. 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.

  2. 假设 f 在 Tg 以上随温度线性增加:\(f = f_g + \alpha_f(T - T_g)\)。

    Assume \(f = f_g + \alpha_f(T - T_g)\).

  3. 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.