Mg-Gd-Y镁合金Zr晶粒细化行为研究
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摘要
镁合金铸造过程中添加有效的晶粒细化剂是非常基础的环节，能显著细化合金组织、提高组织均匀性、减少铸造缺陷，有效改善合金的强韧性和塑性。Zr是不含Al元素的镁合金最有效的细化剂，目前主要是以二元Mg-Zr中间合金的形式加入。近年来，Mg-Gd-Y(-Zr)稀土镁合金因轻质、高强、耐热等优点，在汽车、航空、军工、通讯等领域展现了广阔的应用前景。然而，Zr对Mg-Gd-Y合金晶粒细化行为还未得到全面认识和研究。由于Zr的密度（6.52g/cm~3）重于液态Mg（~1.58g/cm~3），在Mg-Gd-Y镁合金熔炼过程中，Zr的自发沉降引起了晶粒细化的衰退，成为获得稳定晶粒细化效果的瓶颈，因此有必要阐明其衰退行为，以推进Zr细化工艺的发展。更为迫切的问题是，Zr沉降已引起研究者关注原料Zr细化剂的组织特征，特别需要研究Zr中间合金对Mg-Gd-Y细化效果的影响，以探寻更高效的Zr细化剂。同时，一条并行的思路是，研究和开发新型Zr细化剂或加Zr方法，以抑制Zr沉降、节省成本。此外，揭示合金元素Gd、Y、Zr在晶粒细化过程中的交互作用行为，对进一步研究镁合金Zr晶粒细化机制，具有一定的理论意义。
本文研究了Zr对Mg-Gd-Y镁合金晶粒细化行为。通过Zr在Mg-Gd-Y熔体中的沉降实验，揭示了Zr沉降对晶粒细化效果衰退的影响规律，并指出了最佳保温时间。进而通过晶粒细化试验，阐明了Mg-Zr中间合金自身的Zr粒子尺寸分布状态对Mg-Gd-Y镁合金晶粒细化效果的影响，提出了显著改善Mg-30%Zr中间合金细化效果的方法。为抑制Zr沉降和降低成本，开发了针对Mg-Gd-Y镁合金的新型富Zr混合盐原位细化法，并从热力学角度阐明了相关的细化机制。最后，结合实验和理论分析，探讨了合金元素Gd、Y、Zr在该合金晶粒细化过程中的交互作用机制。
沉降实验表明，Zr沉降对Mg-Gd-Y铸锭Zr含量及晶粒尺寸均具有非常不利的影响（衰退）。搅拌结束5min静置至240min，730℃~780℃之间，Zr含量衰退33%，晶粒尺寸粗化23%~27%。沉降计算表明，从搅拌结束静置至5min，主要是大于7μm粒子的沉降，可有效去除尺寸稍大的Zr夹杂，是工艺上需要的沉降；但从5min静置至240min，更细小的Zr粒子沉降占主要作用，是导致晶粒细化衰退的主要原因。
优化的静置工艺为15min。建立了晶粒尺寸粗化率的数学模型：
△C,%=5.21·lnt-8.15(t>5min,730℃),△C,%=6.76.lnt-9.42(t>5min,780℃),
对理解Zr晶粒细化衰退具有一定指导意义。晶粒细化对比实验表明,对于不同的Mg-Zr中间合金,其组织内的Zr粒子尺寸
分布状态,是影响Mg-Gd-Y合金细化效果的主要因素。当Zr中间合金组织中尺寸
5μm以内细小Zr粒子的数量密度最高时,其细化效果最强,因为此区间的Zr粒子
越多,越能在满足溶解Zr量的基础上,提供更多潜在的形核核心。基于此,提出
了多道轧制改善Mg-30%Zr中间合金的Zr粒子分布,细化效果提高30%以上为抑制Zr沉降、节省成本,首次探索了针对Mg-Gd-Y合金的新型富Zr混合盐
原位细化法。提出了优化后的Zr混合盐成分,为50%K2ZrF6-25%NaCl-25%KCl。
对比实验表明,Zr盐细化效果可达到Mg-Zr中间合金的水平,而抗衰退性明显优于
Mg-Zr中间合金。热力学分析揭示了Zr盐细化机制,可能主要由于原位生成的溶质
Zr对Mg晶核的强烈生长抑制作用。阐明了Zr盐法产生的夹杂物是反应产物KF、MgF2和残余盐形成的团簇或结块；
并采用MgO泡沫陶瓷过滤器进行净化除杂,使得铸锭力学性能得到明显提高,但
今后仍有待进一步开发更高效的复合净化工艺以除杂。揭示了晶粒细化过程中,Gd、Y、Zr的交互作用行为。结果表明：未加Zr时,
晶粒尺寸随着Gd、Y含量增加而降低,符合关系式dgs=3894.3·e-0.113·δ(Q为生长
抑制因子)；当Zr含量一定时,晶粒尺寸也是随Gd、Y的增加而降低,但Gd、Y的
增加却降低了Zr对细化的贡献；当Gd、Y含量一定时,晶粒尺寸随Zr含量增加而
降低。对溶解Zr和未溶解Zr的细化贡献分析表明,未溶解Zr粒子异质形核对晶粒
细化的贡献率N(%)随Q增加而降低,基于数据分析构建了之间的数学关系式
n,%=115.8.e-0.111`δ,对进一步研究Zr晶粒细化机制具有一定理论意义。结合Zr异质形核细化贡献的分析(n,%)与活性(active)形核Zr粒子质量分数的计
算,阐明了Gd、Y含量增加抑制了Zr异质形核率的现象。表明一部分潜在形核Zr
粒子并未成功形核,可能是由于溶质扩散场对形核的抑制而造成。
Grain refinement of cast magnesium alloys by inoculation of the melt with potentnucleant particles is the first effective step towards the goal of achieving a fine, uniformand equiaxed grain structure. This imparts to castings critically needed structuraluniformity and consistency in performance improving strength, ductility and so on.Zirconium is the most powerful refiner for Al-free Mg alloys, and the alloying processis normally by adding a binary Mg-Zr master alloy. In recent years, the light, highstrength and heat-resisting Mg-Gd-Y-Zr Mg alloy has attracted a great deal of attentionin the automotive, aviation, military and communication industry. As the density of Zr(~6.52g/cm~3) is much higher than liquid Mg (~1.58g/cm~3), Zr spontaneously settlesdown to the bottom of the crucible and thus this causes grain coarsening and muchwaste. This is an obstacle to development of grain refinement technology of Mg alloys.Therefore, it is very important to study the fading behavior of Zr in the melt, which isbenifical to improve the casting technique and save the usage of Zr. Moreover, thesettling of Zr raises certain concerns for researchers who pay more attention to theinherent quality of Mg-Zr refiners. Therefore, it is very crucial to investigate the effectof Zr master alloys on the grain refinement, which will help develop a more efficient Zrrefiner. Another thought is to develop a new Zr alloying method, which is cost savingand convenient. Furthermore, these studiesm will be useful for us to understand moreabout the grain refinement mechanism of Mg by Zr, if we incorporate the above issueswith the interaction effect of solute Gd, Y and Zr refiner.
In this thesis, the grain refinement technology and mechanism of Mg-Gd-Y alloy byZr was investigated. Based on the settling behavior, the effect of settling of Zr on thefading of grain size was uncovered. The effect of Zr particle distribution in Mg-Zrmaster alloy on grain refinement was explained based on the experiments. Moreover,
the refining efficiency of a Mg-30%Zr master alloy was impoved by hot-rolling. Furthermore, in order to develop an anti-settling and cheap alloying method of Zr, a kind of new Zr-rich salt mixture for Mg-Gd-Y alloy was formulated. The grain refining mechanism of Zr salts mixture is analyzed from thermodynamic aspect. Finally, the interaction effects of Gd, Y and Zr elements during grain refinement were clarified, and the grain refinement mechanism of Zr was discussed.
The settling experiments show that it has an adverse (fading) effect on Zr content and grain size. Within the temperature range of730℃-780℃, when holding from5mins after stirring to240mins, the Zr content decreases by～33%, and the grain size coarsens by23～27%. The settling calcutaion shows that the particles greater than7μm in size settle out of the sample during the first5mins, which is better for removal of Zr clusters. However, the settling of much finer particles plays crucial role when settling time is from5mins to240mins. The optimal holding time is15mins. The dependence of coarsening rate of grain size on the holding time is established by the equations: ΔC,%=5.21·1nt-8.15(t>5min,730℃), ΔC,%=6.76·1tt-9.42(t>5min,780℃). This relationship is instructive to understand the coarsening of Zr grain refinement.
The grain refinement experiments of Mg-Gd-Y alloys by Zr show that the main factor that influences the grain refining effect is the Zr particle size distribution within the microstructure of Mg-Zr master alloy. The master alloy with the largest number density of particles less than5μm in size exhibits the best grain refinement. This is because that those sutiable particles can produce more nucleating sites, when the soluble Zr is of sufficient level. Based on this finding, the particle number density of finer particles within a Mg-30%Zr master alloy has been prepared by hot rolling by8passes from7.5mm to0.5mm. The grain refining efficiency of the Mg-30%Zr is then improved by～30%.
Considering settling problem, a new Zr-rich salts mixture for Zr alloying in Mg-Gd-Y alloy has been developed for the first time. The optimal composition of salts mixture is optimized to be [50%K2ZrF6-25%NaC1-25%KCl](with16.1%Zr inside). Compared with Mg-Zr master alloy, the grain refinement is satisfactory and the fading resistance is much better. Thermodynamic calculations show that the grain refinement of Zr salts is mainly due to the strong grain Growth Restriction Effect/Factor (GRF) of in-situ solute Zr produced by the reaction between Mg melt and Zr salts.
The inclusions followed by chemical reaction of Zr are identified to be the agglomeration of KF, MgF2and the KSM residuals. Filtration purification by Ceramic Foam Filter (CFF) shows that the mechanical properties is slightly improved by-20MPa using the20ppi (pores per inch) MgO CFF, which indicates the purification effect is obvious. However, a more efficient multistage purification technology needs to be developed in future.
The interaction behaviors between Gd, Y and Zr have been disclosed. The results show that the group of alloy without Zr addition has a decreasing grain size with increasing Gd and/or Y contents, and there is a mathematic relationship to show the grain size as following:dgs=3894.3·e-0.113Q, where Q is the value of GRF. The grain size of the group of alloy with an approximately the same Zr content also decreases with the increase in Gd and Y contents, while the increase in Gd and Y content decreases the grain refinement effect of Zr. In addition, the grain size of alloy with certain Gd/Y decreases with the increase in Zr content. The analysis indicates that the nucleating contribution (n,%) of Zr particles to grain refinement decreases with enhancing solute elements (Gd, Y, Zrs), and this effect has been established by the equation:n,%=115.8·e-0.111Q, which has theoretical significance for further investigation of Zr grain refinement mechanism.
Combining the analysis of contribution of Zr to grain refinement with the calculation for weight percentage of active Zr nuclei, it is shown that the nucleation frequency decreases with increasing Gd and/or Y contents. This is possibly because some potential nucleating Zr particles are suppressed by the solute diffusion filed.
本文研究了Zr对Mg-Gd-Y镁合金晶粒细化行为。通过Zr在Mg-Gd-Y熔体中的沉降实验，揭示了Zr沉降对晶粒细化效果衰退的影响规律，并指出了最佳保温时间。进而通过晶粒细化试验，阐明了Mg-Zr中间合金自身的Zr粒子尺寸分布状态对Mg-Gd-Y镁合金晶粒细化效果的影响，提出了显著改善Mg-30%Zr中间合金细化效果的方法。为抑制Zr沉降和降低成本，开发了针对Mg-Gd-Y镁合金的新型富Zr混合盐原位细化法，并从热力学角度阐明了相关的细化机制。最后，结合实验和理论分析，探讨了合金元素Gd、Y、Zr在该合金晶粒细化过程中的交互作用机制。
沉降实验表明，Zr沉降对Mg-Gd-Y铸锭Zr含量及晶粒尺寸均具有非常不利的影响（衰退）。搅拌结束5min静置至240min，730℃~780℃之间，Zr含量衰退33%，晶粒尺寸粗化23%~27%。沉降计算表明，从搅拌结束静置至5min，主要是大于7μm粒子的沉降，可有效去除尺寸稍大的Zr夹杂，是工艺上需要的沉降；但从5min静置至240min，更细小的Zr粒子沉降占主要作用，是导致晶粒细化衰退的主要原因。
优化的静置工艺为15min。建立了晶粒尺寸粗化率的数学模型：
△C,%=5.21·lnt-8.15(t>5min,730℃),△C,%=6.76.lnt-9.42(t>5min,780℃),
对理解Zr晶粒细化衰退具有一定指导意义。晶粒细化对比实验表明,对于不同的Mg-Zr中间合金,其组织内的Zr粒子尺寸
分布状态,是影响Mg-Gd-Y合金细化效果的主要因素。当Zr中间合金组织中尺寸
5μm以内细小Zr粒子的数量密度最高时,其细化效果最强,因为此区间的Zr粒子
越多,越能在满足溶解Zr量的基础上,提供更多潜在的形核核心。基于此,提出
了多道轧制改善Mg-30%Zr中间合金的Zr粒子分布,细化效果提高30%以上为抑制Zr沉降、节省成本,首次探索了针对Mg-Gd-Y合金的新型富Zr混合盐
原位细化法。提出了优化后的Zr混合盐成分,为50%K2ZrF6-25%NaCl-25%KCl。
对比实验表明,Zr盐细化效果可达到Mg-Zr中间合金的水平,而抗衰退性明显优于
Mg-Zr中间合金。热力学分析揭示了Zr盐细化机制,可能主要由于原位生成的溶质
Zr对Mg晶核的强烈生长抑制作用。阐明了Zr盐法产生的夹杂物是反应产物KF、MgF2和残余盐形成的团簇或结块；
并采用MgO泡沫陶瓷过滤器进行净化除杂,使得铸锭力学性能得到明显提高,但
今后仍有待进一步开发更高效的复合净化工艺以除杂。揭示了晶粒细化过程中,Gd、Y、Zr的交互作用行为。结果表明：未加Zr时,
晶粒尺寸随着Gd、Y含量增加而降低,符合关系式dgs=3894.3·e-0.113·δ(Q为生长
抑制因子)；当Zr含量一定时,晶粒尺寸也是随Gd、Y的增加而降低,但Gd、Y的
增加却降低了Zr对细化的贡献；当Gd、Y含量一定时,晶粒尺寸随Zr含量增加而
降低。对溶解Zr和未溶解Zr的细化贡献分析表明,未溶解Zr粒子异质形核对晶粒
细化的贡献率N(%)随Q增加而降低,基于数据分析构建了之间的数学关系式
n,%=115.8.e-0.111`δ,对进一步研究Zr晶粒细化机制具有一定理论意义。结合Zr异质形核细化贡献的分析(n,%)与活性(active)形核Zr粒子质量分数的计
算,阐明了Gd、Y含量增加抑制了Zr异质形核率的现象。表明一部分潜在形核Zr
粒子并未成功形核,可能是由于溶质扩散场对形核的抑制而造成。
Grain refinement of cast magnesium alloys by inoculation of the melt with potentnucleant particles is the first effective step towards the goal of achieving a fine, uniformand equiaxed grain structure. This imparts to castings critically needed structuraluniformity and consistency in performance improving strength, ductility and so on.Zirconium is the most powerful refiner for Al-free Mg alloys, and the alloying processis normally by adding a binary Mg-Zr master alloy. In recent years, the light, highstrength and heat-resisting Mg-Gd-Y-Zr Mg alloy has attracted a great deal of attentionin the automotive, aviation, military and communication industry. As the density of Zr(~6.52g/cm~3) is much higher than liquid Mg (~1.58g/cm~3), Zr spontaneously settlesdown to the bottom of the crucible and thus this causes grain coarsening and muchwaste. This is an obstacle to development of grain refinement technology of Mg alloys.Therefore, it is very important to study the fading behavior of Zr in the melt, which isbenifical to improve the casting technique and save the usage of Zr. Moreover, thesettling of Zr raises certain concerns for researchers who pay more attention to theinherent quality of Mg-Zr refiners. Therefore, it is very crucial to investigate the effectof Zr master alloys on the grain refinement, which will help develop a more efficient Zrrefiner. Another thought is to develop a new Zr alloying method, which is cost savingand convenient. Furthermore, these studiesm will be useful for us to understand moreabout the grain refinement mechanism of Mg by Zr, if we incorporate the above issueswith the interaction effect of solute Gd, Y and Zr refiner.
In this thesis, the grain refinement technology and mechanism of Mg-Gd-Y alloy byZr was investigated. Based on the settling behavior, the effect of settling of Zr on thefading of grain size was uncovered. The effect of Zr particle distribution in Mg-Zrmaster alloy on grain refinement was explained based on the experiments. Moreover,
the refining efficiency of a Mg-30%Zr master alloy was impoved by hot-rolling. Furthermore, in order to develop an anti-settling and cheap alloying method of Zr, a kind of new Zr-rich salt mixture for Mg-Gd-Y alloy was formulated. The grain refining mechanism of Zr salts mixture is analyzed from thermodynamic aspect. Finally, the interaction effects of Gd, Y and Zr elements during grain refinement were clarified, and the grain refinement mechanism of Zr was discussed.
The settling experiments show that it has an adverse (fading) effect on Zr content and grain size. Within the temperature range of730℃-780℃, when holding from5mins after stirring to240mins, the Zr content decreases by～33%, and the grain size coarsens by23～27%. The settling calcutaion shows that the particles greater than7μm in size settle out of the sample during the first5mins, which is better for removal of Zr clusters. However, the settling of much finer particles plays crucial role when settling time is from5mins to240mins. The optimal holding time is15mins. The dependence of coarsening rate of grain size on the holding time is established by the equations: ΔC,%=5.21·1nt-8.15(t>5min,730℃), ΔC,%=6.76·1tt-9.42(t>5min,780℃). This relationship is instructive to understand the coarsening of Zr grain refinement.
The grain refinement experiments of Mg-Gd-Y alloys by Zr show that the main factor that influences the grain refining effect is the Zr particle size distribution within the microstructure of Mg-Zr master alloy. The master alloy with the largest number density of particles less than5μm in size exhibits the best grain refinement. This is because that those sutiable particles can produce more nucleating sites, when the soluble Zr is of sufficient level. Based on this finding, the particle number density of finer particles within a Mg-30%Zr master alloy has been prepared by hot rolling by8passes from7.5mm to0.5mm. The grain refining efficiency of the Mg-30%Zr is then improved by～30%.
Considering settling problem, a new Zr-rich salts mixture for Zr alloying in Mg-Gd-Y alloy has been developed for the first time. The optimal composition of salts mixture is optimized to be [50%K2ZrF6-25%NaC1-25%KCl](with16.1%Zr inside). Compared with Mg-Zr master alloy, the grain refinement is satisfactory and the fading resistance is much better. Thermodynamic calculations show that the grain refinement of Zr salts is mainly due to the strong grain Growth Restriction Effect/Factor (GRF) of in-situ solute Zr produced by the reaction between Mg melt and Zr salts.
The inclusions followed by chemical reaction of Zr are identified to be the agglomeration of KF, MgF2and the KSM residuals. Filtration purification by Ceramic Foam Filter (CFF) shows that the mechanical properties is slightly improved by-20MPa using the20ppi (pores per inch) MgO CFF, which indicates the purification effect is obvious. However, a more efficient multistage purification technology needs to be developed in future.
The interaction behaviors between Gd, Y and Zr have been disclosed. The results show that the group of alloy without Zr addition has a decreasing grain size with increasing Gd and/or Y contents, and there is a mathematic relationship to show the grain size as following:dgs=3894.3·e-0.113Q, where Q is the value of GRF. The grain size of the group of alloy with an approximately the same Zr content also decreases with the increase in Gd and Y contents, while the increase in Gd and Y content decreases the grain refinement effect of Zr. In addition, the grain size of alloy with certain Gd/Y decreases with the increase in Zr content. The analysis indicates that the nucleating contribution (n,%) of Zr particles to grain refinement decreases with enhancing solute elements (Gd, Y, Zrs), and this effect has been established by the equation:n,%=115.8·e-0.111Q, which has theoretical significance for further investigation of Zr grain refinement mechanism.
Combining the analysis of contribution of Zr to grain refinement with the calculation for weight percentage of active Zr nuclei, it is shown that the nucleation frequency decreases with increasing Gd and/or Y contents. This is possibly because some potential nucleating Zr particles are suppressed by the solute diffusion filed.
引文
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