温度及其波动对橡胶密封硫化过程影响的仿真分析

doi:10.11949/0438-1157.20231213

摘要/Abstract

摘要：

硫化是橡胶密封成型过程的关键工艺，对橡胶密封产品性能有决定性影响。目前橡胶行业多采用经验式硫化成型方法，对橡胶密封硫化演变过程缺乏理解，难以理论指导橡胶密封实际生产过程。针对这一制约橡胶密封质量提升的薄弱环节，开展了橡胶密封硫化成型过程数值仿真研究。基于胶料的积分型反应动力学模型与变物性参数传热控制方程，建立了橡胶制品热-化学耦合的瞬态仿真模型，实现了橡胶制品成型过程时变温度场及硫化程度场的实时预测，并通过试验验证了模型及求解方法的正确性。进而，仿真分析了典型结构密封件的硫化过程，探讨了模具温度、胶料预热温度和温度波动行为对橡胶密封硫化成型过程的影响规律，最后为橡胶密封实际硫化生产提供了参考。

关键词: 橡胶密封, 加工制造, 反应动力学, 温度波动, 数值分析

Abstract:

As a key process in the rubber sealing molding, vulcanization has a significant impact on the performance of rubber sealing products. However, the rubber industry often adopts empirical vulcanization molding methods, lacking understanding of the evolution of vulcanization, making it difficult to theoretically guide the actual production process of rubber seals. In response to this weak link that restricts the improvement of rubber sealing quality, the paper conducted numerical simulation research on the vulcanization molding process of rubber seals. A transient simulation model for thermal-chemical coupling of rubber products was established based on an integral reaction kinetics model and a heat transfer control equation with variable physical parameters. Real time prediction of the time-varying temperature field and vulcanization degree field during the rubber product forming process was achieved, and the correctness of the model and solution method was verified through experiments. Furthermore, the vulcanization process of typical structural seals was simulated and analyzed, and the influence of mold temperature, rubber preheating temperature and temperature fluctuation behavior on the rubber seal vulcanization molding process was discussed. Finally, suggestions and references were provided for the actual vulcanization production of rubber seals.

Key words: rubber seals, fabrication, reaction kinetics, temperature fluctuations, numerical analysis

中图分类号:

TQ 330.67

张兆想, 蔡茂坤, 任志英, 贾晓红, 郭飞. 温度及其波动对橡胶密封硫化过程影响的仿真分析[J]. 化工学报, 2024, 75(2): 715-726.

Zhaoxiang ZHANG, Maokun CAI, Zhiying REN, Xiaohong JIA, Fei GUO. Numerical analysis of the effect of temperature and its fluctuations on the vulcanization process of rubber seals[J]. CIESC Journal, 2024, 75(2): 715-726.

图/表 17

表1 EPDM-60橡胶热硫化期反应动力学模型参数

Table 1 Parameters of the reaction kinetics model for EPDM-60 rubber during vulcanization period

参数	数值/公式（160~185℃）
E_a /R	16606.73
h(α)	$\begin{array}{l} h (α) = - 8.072 \times 10^{- 16} + 3.90698 \times \\ 10^{- 21} e^{(α - 0.48202) / 0.03156} + \\ 1.20495 \times 10^{- 14} e^{(α - 0.48202) / 0.29952} \end{array}$
h′(α)	$\begin{array}{l} h^{'} (α) = \frac{3.90698 \times 10^{- 21}}{0.03156} e^{(α - 0.48202) / 0.03156} + \\ \frac{1.20495 \times 10^{- 14}}{0.29952} e^{(α - 0.48202) / 0.29952} \end{array}$

表1 EPDM-60橡胶热硫化期反应动力学模型参数

Table 1 Parameters of the reaction kinetics model for EPDM-60 rubber during vulcanization period

参数	数值/公式（160~185℃）
E_a /R	16606.73
h(α)	$\begin{array}{l} h (α) = - 8.072 \times 10^{- 16} + 3.90698 \times \\ 10^{- 21} e^{(α - 0.48202) / 0.03156} + \\ 1.20495 \times 10^{- 14} e^{(α - 0.48202) / 0.29952} \end{array}$
h′(α)	$\begin{array}{l} h^{'} (α) = \frac{3.90698 \times 10^{- 21}}{0.03156} e^{(α - 0.48202) / 0.03156} + \\ \frac{1.20495 \times 10^{- 14}}{0.29952} e^{(α - 0.48202) / 0.29952} \end{array}$

图1 模型计算曲线与试验曲线对比

Fig.1 Comparison between model calculation curve and experimental curve

表2 EPDM-60热物性参数与硫化程度及温度间关系式

Table 2 Relationship between EPDM-60 thermophysical parameters and degree of vulcanization and temperature

参数	关系式
比定压热容/(J/(kg·K))	$\begin{array}{l} c_{p} (α, T) = 2806.51 - 3567.18 α + \\ 2400.64 α^{2} + 7.22 T - 6.76 \times \\ 10^{- 3} T^{2} - 4.76 α T \end{array}$
热导率/(W/(m·K))	$\begin{array}{l} k (α, T) = 0.23586 + 0.15850 α + 0.15146 α^{2} - \\ 0.24368 α^{3} - 1.38146 \times 10^{- 4} T - \\ 1.83456 \times 10^{- 7} T^{2} \end{array}$

表2 EPDM-60热物性参数与硫化程度及温度间关系式

Table 2 Relationship between EPDM-60 thermophysical parameters and degree of vulcanization and temperature

参数	关系式
比定压热容/(J/(kg·K))	$\begin{array}{l} c_{p} (α, T) = 2806.51 - 3567.18 α + \\ 2400.64 α^{2} + 7.22 T - 6.76 \times \\ 10^{- 3} T^{2} - 4.76 α T \end{array}$
热导率/(W/(m·K))	$\begin{array}{l} k (α, T) = 0.23586 + 0.15850 α + 0.15146 α^{2} - \\ 0.24368 α^{3} - 1.38146 \times 10^{- 4} T - \\ 1.83456 \times 10^{- 7} T^{2} \end{array}$

图2 橡胶硫化瞬态传热-硫化耦合有限元模型求解示意

Fig.2 Solution schematic of transient heat transfer vulcanization coupling finite element model for rubber vulcanization

图3 橡胶硫化过程传热-硫化耦合求解子程序流程图

Fig.3 Subprogram for heat transfer vulcanization coupling solution in rubber vulcanization process

图4 圆柱形硫化试样切面

Fig.4 Sectional view of cylindrical vulcanized specimen

图5 不同时间下试样各区域的DSC测试曲线

Fig.5 DSC test curves of different regions of the sample at different times

图6 圆柱形橡胶硫化计算结果

Fig.6 Calculation results of cylindrical rubber vulcanization

图7 不同硫化时间生产圆柱形橡胶试样试验与仿真结果对比

Fig.7 Comparison of experimental and simulation results for producing cylindrical rubber samples

图8 本研究密封件结构示意

Fig.8 Schematic diagram of seal structure in the study

图9 不同尺寸的密封件在各模具温度下的硫化过程

Fig.9 Vulcanization process of seals of different sizes at different mold temperatures

图10 不同尺寸和密封方式密封硫化90%时所需时间

Fig.10 Times required for different sizes and seal methods of seals to achieve 90% vulcanization

图11 不同预热温度下尺寸20 mm的密封件在175℃下硫化过程对比

Fig.11 Comparison of vulcanization process of seals with a size of 20 mm at 175℃ with different preheating temperatures

图12 预热前后O形密封件中心处温度与硫化程度对比

Fig.12 Comparison of temperature and vulcanization degree at the center of the O-ring seal before and after preheating

图13 模具温度在不同调节频率下的波动示意

Fig.13 Schematic diagram of mold temperature fluctuations at different adjustment frequencies

图14 截面直径5 mm的O形密封件在不同温度波动情况下的硫化情况

Fig.14 Vulcanization of O-ring seals with a cross-sectional diameter of 5 mm under different temperature fluctuations

图15 截面直径20 mm的O形密封件在不同温度波动情况下的硫化情况

Fig.15 Vulcanization of O-ring seals with a cross-sectional diameter of 20 mm under different temperature fluctuations

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