锌铝合金的组织性能优化及相关基础研究
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摘要
摘要：本文针对我国炼锌企业在开发高性能锌铝合金面临的技术瓶颈,瞄准国际上锌铝合金研究开发的最新发展趋势,分别对压铸锌铝合金、重力铸造锌铝合金以及热镀锌铝合金展开研究,为生产出符合市场需求的高性能锌铝合金提供技术支撑,对我国资源的综合利用及现代化工业建设具有重要的现实意义。
锌铝合金具有熔点低、熔炼耗能少、流动性好、常温强度优良等特点,可以满足不同用户的使用需求,具有很强的市场竞争力。然而国产锌铝合金普遍存在塑韧性较差、杂质含量高、尺寸稳定性差、耐蚀性较差等缺陷,因此开展锌铝合金的相关基础研究和应用技术研究具有重要意义。论文采用金相、扫描电镜、X射线衍射以及流动性测试、力学性能测试、耐蚀性测试等方法,系统研究了不同Al含量对锌铝合金流动性、力学性能以及耐腐蚀性能的影响,微合金化对ZnAl4压铸锌铝合金的微观组织及力学性能的影响,热变形、热处理对ZA27重力铸造锌铝合金微观组织及力学性能的影响,以及RE对Zn-5%Al合金耐蚀性的影响。主要结论如下：
1.研究了不同Al量对锌铝合金微观组织、流动性、力学性能以及耐腐蚀性能的影响,结果表明,当Al含量为4%时,合金流动性较好,抗拉强度较高,适用于压铸力学性能要求不高的零部件,当Al含量为27%时,合金抗拉强度最高,适用于制备具有一定性能要求的零部件,当Al含量为5%时,合金流动性好、耐蚀性好,适用于制备防腐用镀层。
2.研究了微量Zr、Sr对ZnA14合金硬度、抗拉强度、冲击韧度以及微观组织的影响,结果表明,Zr可有效细化η-Zn枝晶,缩短枝晶网胞间层片组织的片层间距,Zr与Al、Zn原子反应,在枝晶网胞间生成Al2ZnZr,起到钉扎晶界的作用,Zr还可俘获杂质元素Fe,降低杂质Fe对合金性能的有害影响,当Zr的添加量为0.1%时,实验合金的综合力学性能最好。Sr有效细化η-Zn枝晶,Sr还与Zn结合生成SrZn13,起到钉扎晶界的作用,当Sr的添加量为0.1%时,实验合金的综合力学性能最好。
3.采用FLOW-3D压铸模拟软件,通过表面缺陷追踪模拟分析,确定了ZnAl4合金充型过程中各阶段的氧化夹杂的位置。通过正交压铸模拟试验,分别得出温度场、应力场、速度场以及表面缺陷分布状况的模拟结果,确定了最佳的压铸工艺参数：浇注温度为420℃,压射速度为2.5m/s,模具温度200℃。
4.通过热压缩实验研究ZA27合金的热变形行为,得到了不同变形温度和应变速率条件的真应力-真应变曲线,建立了ZA27合金热塑性变形的流变应力数学模型,推导出了用Z参数表达的流变应力方程：根据实验结果计算出的材料常数：n=5.21, a=0.007, A=1.81×l010s-1,变形激活能Q=109.39kJ/mol, Z=εexp(13157/T)。采用改进的Arrhenius模型及人工神经网络模型建立了ZA27合金的本构关系,并在实验条件内进行验证,人工神经网络模型可更好地反映ZA27合金的热变形行为。结合热加工图分析及微观组织观察结果,合金的最佳热加工参数区为250～350℃的变形温度和0.1～1s-1的应变速率。
5.确定了ZA27合金的最佳热处理工艺,最佳均匀化工艺为360℃/12h,炉冷,枝晶偏析及非平衡共晶相基本消除,塑性得到有效改善。最佳固溶工艺为365℃/1h,水淬,实验合金得以充分固溶,α相、η相基本溶入基体。较优的时效工艺为140℃/1h,空冷,时效析出相数量多、尺寸小、分布均匀,合金的综合力学性能得到显著提高。
6.研究了不同含量RE对Zn-5%Al合金镀层耐蚀性的影响,Zn-5%Al-RE系合金镀层在中性盐雾实验条件下的腐蚀产物主要为ZnO、Zn(OH)2、Zn5(OH)8Cl2·H2O、Zn5(OH)6(CO3)2、Al2(OH)5Cl·2H2O。当RE的添加量达到0.1%后,随着RE含量的增加,镀层的自腐蚀电流密度逐渐下降,当RE的添加量为0.6%时,腐蚀产物结构致密细小且均匀,自腐蚀电流密度最低,电荷转移电阻Rct最小,耐蚀性最好。
Abstract:Aiming at the latest development trends in the world on developing high-performance zinc aluminum alloy, we have developed basic research and applied technology research in pressure casting zinc aluminum alloy, gravity casting zinc aluminum alloy and hot-dip zinc aluminum alloy, respectively, for the purpose of offering technological supports for producing high-performance zinc aluminum alloy which can meet the market demands. This study is of great significance in comprehensive utilizing of zinc resource and modernization of industry in our country.
The zinc aluminum alloy can meet different users' demands with strong market competitiveness, as it has low melting point and fusion energy dissipation, good fluidity as well as excellent room-temperature mechanical properties. However, the domestic zinc aluminum alloy have common defects such as low plasticity and toughness, high impurities, low dimension instability as well as low corrosion resistance, so it is of great significance to develop basic research study. The effects of Al on the fluidity, mechanical properties and corrosion resistance of zinc aluminum alloy were studied, the effects of alloying on the microstructure and mechanical properties and the die casting processing of ZnA14die casting alloy were studied, then the effects of hot deformation and heat treatment on microstructure and mechanical properties of ZA27alloy were studied. Moreover, the effects of RE on the corrosion resistance of Zn-5%Al hot dipped zinc aluminum alloy were studied. The major conclusions were drawn as follows.
1. The effects of Al on the microstructure, fluidity, mechanical properties and corrosion resistance of Zn-Al alloy were studied, the results show that ZnA14alloy has good fluidity and tensile strength, ZA27alloy has the best tensile strength, Zn-5%Al alloy has good fluidity and corrosion resistance.
2. The effects of rare Zr and Sr on the microstructure and mechanical properties of ZnA14alloy were studied, the results show that Zr can effectively refine the η-Zn dendrite and shorten the lamellar spacing. The
Al2ZnZr compounds can be formed between the cellular-dendrite structure and pining the grain boundary effectively. Moreover, Zr can trap the impurity of Fe and eliminate the harmful influence of Fe on the properties of ZnA14alloy. When adding0.1%Zr, the alloy has perfect comprehensive properties. Adding element Sr into the alloy results the formation of SrZn13compounds, the primary η-Zn phase is restrained. When adding0.1%Sr, the alloy has perfect comprehensive properties.
3. The die casting filling process of ZnA14alloy shell part has been simulated with FLOW-3D software. The die casting processing parameters can be optimized with the help of orthogonal experiment. The simulation results of temperature field, velocity field, pressure field and surface defect concentration show that the optimized processing parameter is pouring temperature420℃, injection speed2.5m/s, mold initial temperature200℃.
4. The hot deformation behavior of ZA27alloy was investigated by hot compression tests. One linear regression equation with Z constant has been proposed as the following:
Where n=5.21,α=0.007, A=1.81×1010s-1, Q=109.39kJ/mol and Z=εexp(13157/T). A comparative evaluation of the trained ANN model and the constitutive equations has been carried out. It is found that the trained ANN model is more efficient and accurate in predicting the hot deformation behavior of ZA27alloy. Based on the processing map and deformed microstructure, the hot deformation of ZA27alloy can be carried out safely in the region with a strain rate of0.1～1s-1and temperature range of250-350℃.
5. The optimal heat treatment conditions of ZA27alloy are as follows:
After annealing at360℃for24h, the non-equilibrium βphases at the grain boundaries and the dendritic segregation are eliminated. After solution treatment at365℃for1h, complete dissolution of the solute atoms is obtained. After ageing at140℃for1h, fine uniformly precipitates are obtained, and the Comprehensive mechanical properties are improved significantly.
6. The effects of Re on the corrosion behaviors of Zn-5%Al hot dipped zinc aluminum alloys were studied by SEM, electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization. The results show that ZnO, Zn5(OH)8Cl2·H2O, Zn5(OH)6(CO3)2and Al2(OH)sCl·2H2O are the main corrosion products of Zn-5%Al-RE coatings. By comparing the corrosion behavior of the Zn-5%Al-RE coatings, the corrosion layer formed on Zn-5%A1-0.6%RE coating is more compact than the other coatings and has the best corrosion resistance.
锌铝合金具有熔点低、熔炼耗能少、流动性好、常温强度优良等特点,可以满足不同用户的使用需求,具有很强的市场竞争力。然而国产锌铝合金普遍存在塑韧性较差、杂质含量高、尺寸稳定性差、耐蚀性较差等缺陷,因此开展锌铝合金的相关基础研究和应用技术研究具有重要意义。论文采用金相、扫描电镜、X射线衍射以及流动性测试、力学性能测试、耐蚀性测试等方法,系统研究了不同Al含量对锌铝合金流动性、力学性能以及耐腐蚀性能的影响,微合金化对ZnAl4压铸锌铝合金的微观组织及力学性能的影响,热变形、热处理对ZA27重力铸造锌铝合金微观组织及力学性能的影响,以及RE对Zn-5%Al合金耐蚀性的影响。主要结论如下：
1.研究了不同Al量对锌铝合金微观组织、流动性、力学性能以及耐腐蚀性能的影响,结果表明,当Al含量为4%时,合金流动性较好,抗拉强度较高,适用于压铸力学性能要求不高的零部件,当Al含量为27%时,合金抗拉强度最高,适用于制备具有一定性能要求的零部件,当Al含量为5%时,合金流动性好、耐蚀性好,适用于制备防腐用镀层。
2.研究了微量Zr、Sr对ZnA14合金硬度、抗拉强度、冲击韧度以及微观组织的影响,结果表明,Zr可有效细化η-Zn枝晶,缩短枝晶网胞间层片组织的片层间距,Zr与Al、Zn原子反应,在枝晶网胞间生成Al2ZnZr,起到钉扎晶界的作用,Zr还可俘获杂质元素Fe,降低杂质Fe对合金性能的有害影响,当Zr的添加量为0.1%时,实验合金的综合力学性能最好。Sr有效细化η-Zn枝晶,Sr还与Zn结合生成SrZn13,起到钉扎晶界的作用,当Sr的添加量为0.1%时,实验合金的综合力学性能最好。
3.采用FLOW-3D压铸模拟软件,通过表面缺陷追踪模拟分析,确定了ZnAl4合金充型过程中各阶段的氧化夹杂的位置。通过正交压铸模拟试验,分别得出温度场、应力场、速度场以及表面缺陷分布状况的模拟结果,确定了最佳的压铸工艺参数：浇注温度为420℃,压射速度为2.5m/s,模具温度200℃。
4.通过热压缩实验研究ZA27合金的热变形行为,得到了不同变形温度和应变速率条件的真应力-真应变曲线,建立了ZA27合金热塑性变形的流变应力数学模型,推导出了用Z参数表达的流变应力方程：根据实验结果计算出的材料常数：n=5.21, a=0.007, A=1.81×l010s-1,变形激活能Q=109.39kJ/mol, Z=εexp(13157/T)。采用改进的Arrhenius模型及人工神经网络模型建立了ZA27合金的本构关系,并在实验条件内进行验证,人工神经网络模型可更好地反映ZA27合金的热变形行为。结合热加工图分析及微观组织观察结果,合金的最佳热加工参数区为250～350℃的变形温度和0.1～1s-1的应变速率。
5.确定了ZA27合金的最佳热处理工艺,最佳均匀化工艺为360℃/12h,炉冷,枝晶偏析及非平衡共晶相基本消除,塑性得到有效改善。最佳固溶工艺为365℃/1h,水淬,实验合金得以充分固溶,α相、η相基本溶入基体。较优的时效工艺为140℃/1h,空冷,时效析出相数量多、尺寸小、分布均匀,合金的综合力学性能得到显著提高。
6.研究了不同含量RE对Zn-5%Al合金镀层耐蚀性的影响,Zn-5%Al-RE系合金镀层在中性盐雾实验条件下的腐蚀产物主要为ZnO、Zn(OH)2、Zn5(OH)8Cl2·H2O、Zn5(OH)6(CO3)2、Al2(OH)5Cl·2H2O。当RE的添加量达到0.1%后,随着RE含量的增加,镀层的自腐蚀电流密度逐渐下降,当RE的添加量为0.6%时,腐蚀产物结构致密细小且均匀,自腐蚀电流密度最低,电荷转移电阻Rct最小,耐蚀性最好。
Abstract:Aiming at the latest development trends in the world on developing high-performance zinc aluminum alloy, we have developed basic research and applied technology research in pressure casting zinc aluminum alloy, gravity casting zinc aluminum alloy and hot-dip zinc aluminum alloy, respectively, for the purpose of offering technological supports for producing high-performance zinc aluminum alloy which can meet the market demands. This study is of great significance in comprehensive utilizing of zinc resource and modernization of industry in our country.
The zinc aluminum alloy can meet different users' demands with strong market competitiveness, as it has low melting point and fusion energy dissipation, good fluidity as well as excellent room-temperature mechanical properties. However, the domestic zinc aluminum alloy have common defects such as low plasticity and toughness, high impurities, low dimension instability as well as low corrosion resistance, so it is of great significance to develop basic research study. The effects of Al on the fluidity, mechanical properties and corrosion resistance of zinc aluminum alloy were studied, the effects of alloying on the microstructure and mechanical properties and the die casting processing of ZnA14die casting alloy were studied, then the effects of hot deformation and heat treatment on microstructure and mechanical properties of ZA27alloy were studied. Moreover, the effects of RE on the corrosion resistance of Zn-5%Al hot dipped zinc aluminum alloy were studied. The major conclusions were drawn as follows.
1. The effects of Al on the microstructure, fluidity, mechanical properties and corrosion resistance of Zn-Al alloy were studied, the results show that ZnA14alloy has good fluidity and tensile strength, ZA27alloy has the best tensile strength, Zn-5%Al alloy has good fluidity and corrosion resistance.
2. The effects of rare Zr and Sr on the microstructure and mechanical properties of ZnA14alloy were studied, the results show that Zr can effectively refine the η-Zn dendrite and shorten the lamellar spacing. The
Al2ZnZr compounds can be formed between the cellular-dendrite structure and pining the grain boundary effectively. Moreover, Zr can trap the impurity of Fe and eliminate the harmful influence of Fe on the properties of ZnA14alloy. When adding0.1%Zr, the alloy has perfect comprehensive properties. Adding element Sr into the alloy results the formation of SrZn13compounds, the primary η-Zn phase is restrained. When adding0.1%Sr, the alloy has perfect comprehensive properties.
3. The die casting filling process of ZnA14alloy shell part has been simulated with FLOW-3D software. The die casting processing parameters can be optimized with the help of orthogonal experiment. The simulation results of temperature field, velocity field, pressure field and surface defect concentration show that the optimized processing parameter is pouring temperature420℃, injection speed2.5m/s, mold initial temperature200℃.
4. The hot deformation behavior of ZA27alloy was investigated by hot compression tests. One linear regression equation with Z constant has been proposed as the following:
Where n=5.21,α=0.007, A=1.81×1010s-1, Q=109.39kJ/mol and Z=εexp(13157/T). A comparative evaluation of the trained ANN model and the constitutive equations has been carried out. It is found that the trained ANN model is more efficient and accurate in predicting the hot deformation behavior of ZA27alloy. Based on the processing map and deformed microstructure, the hot deformation of ZA27alloy can be carried out safely in the region with a strain rate of0.1～1s-1and temperature range of250-350℃.
5. The optimal heat treatment conditions of ZA27alloy are as follows:
After annealing at360℃for24h, the non-equilibrium βphases at the grain boundaries and the dendritic segregation are eliminated. After solution treatment at365℃for1h, complete dissolution of the solute atoms is obtained. After ageing at140℃for1h, fine uniformly precipitates are obtained, and the Comprehensive mechanical properties are improved significantly.
6. The effects of Re on the corrosion behaviors of Zn-5%Al hot dipped zinc aluminum alloys were studied by SEM, electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization. The results show that ZnO, Zn5(OH)8Cl2·H2O, Zn5(OH)6(CO3)2and Al2(OH)sCl·2H2O are the main corrosion products of Zn-5%Al-RE coatings. By comparing the corrosion behavior of the Zn-5%Al-RE coatings, the corrosion layer formed on Zn-5%A1-0.6%RE coating is more compact than the other coatings and has the best corrosion resistance.
引文
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