稀土镁合金组织和性能研究
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摘要
基于对耐蚀、高强韧镁合金材料的需求，本文研究了Gd、Nd和Y等稀土元素对镁合金耐蚀性能和力学性能的影响规律，并具体结合两类不同的稀土镁合金，研究了铸造、热处理和热挤压变形等工艺对合金组织和性能的影响。
通过研究稀土元素对镁合金耐蚀性的影响机制发现：添加稀土元素后形成的第二相与镁基体的镁合金的电极电位差变小，导致微电偶腐蚀的驱动力相应减弱，微电偶腐蚀的极化电流变小，腐蚀速率降低；稀土元素可以通过改变金属表面氧化膜的结构提高致密度、细化晶粒、改变了镁合金中第二相的组成、形态和分布等，从而改善了镁合金耐腐蚀性。
稀土镁合金材料制备工艺过程中，保持成分均匀稳定、减少熔剂夹杂和熔体吹洗等途径有利于合金耐蚀性的改善；挤压铸造、金属型铸造和砂型铸造三种方法相比，挤压铸造制备的合金组织晶粒更细、力学性能和耐蚀性更好。
对两类不同稀土含量的镁合金的压缩应力应变行为的研究表明二者均是正应变速率敏感材料，合金热压缩塑性变形是受热激活控制的。
对Mg-Nd-Gd-Zn-Zr合金的研究表明，通过成分设计可以实现低稀土含量的镁合金具有良好的耐蚀性，铸态合金通过合理的热处理工艺可以实现强度和伸长率的综合优化；由于稀土含量不高，挤压变形后的合金经时效处理时析出强化效果有限，位错与稀土第二相的交互作用不明显。
高稀土含量的Mg-xGd-3Y-Zn-0.5Zr合金的铸态组织由α-Mg和β相（Mg_5Gd(Y,Zn)）组成，且随着Gd含量的增加，晶粒尺寸呈细化趋势，晶界共晶相由连续网状分布转变为断续状弥散分布，且共晶相数量也相应增加。合金经固溶处理后，合金晶界β相（Mg_5Gd(Y,Zn)分解并生成成分有序和堆垛有序的块状、层片状的14H-LPSO结构相，这些LPSO相是由Mg、Zn、Gd和Y元素组成，而Zn是形成14H-LPSO的关键合金元素。合金时效峰值硬度随Gd含量的增加而增高，到达峰值硬度的时间随Gd含量的增加而缩短；随温度升高，峰值硬度降低，到达峰值硬度的时间缩短。8%wtGd的合金200℃时效析出弥散分布的β'相，而250℃时效未发现明显的弥散析出相。12wt%Gd的合金随时效温度的升高，峰值硬化组织时效析出β'相尺寸增大，数量减少；在200℃和225℃的时效硬化归因为高致密分布的β'相；在250℃的峰值硬化组织析出相是β'相和β1，后随时间延长β'相逐渐向β1转变。
对铸造Mg-xGd-3Y-Zn-0.5Zr合金的力学性能研究发现，常温抗拉强度接近，伸长率对Gd含量增加而降低。Gd含量不低于10wt%的合金的抗拉强度在室温~200℃呈增加趋势并在200℃附近达到最大，随后逐渐下降。对合金失效断口分析发现，合金在室温的断裂主要是解理断裂且随Gd含量的增加脆性增加，高温断裂表现为准解理断裂。
Mg-xGd-3Y-Zn-0.5Zr合金经过挤压变形后晶粒显著细化，挤压合金时效强化效应显著，合金力学性能最高时强度和伸长率分别为492MPa和11%，具有良好的塑韧性。
To meet the demand of corrosion-resistant and high-strength magnesium alloy,this paper was engaged in the study of the effects and influence mechanisms of Rareearth (RE) to the corrosion-resistant performance and mechanical properties. Twokinds of alloys with different RE contents were involved to study the influence ofcasting, heat treatment and hot-extrusion deformation processes to the microstructuresand properties of the alloys.
By investigating the influence mechanism of RE elements to thecorrosion-resistant performance of Mg alloy, it shows that, the voltage between theMg matrix and the RE second phases is decreased and the driving force of microelectrical-couple corrosion became weak and corrosion rate was dropped; thecorrosion-resistant performance was improved by the RE elements through the meansof optimizing the structure of the oxidation film to increase the film density, refiningthe grain size, changing the composition, shape and distribution of the second phases.
The approaches of guaranting the stability of the RE Mg alloy, reducing the fluximpurities and gas purifying the melt were helpful to improve the corrosion-resistantperformance of the RE Mg alloy. Among the three methods of the squeeze casting,metal mold casting and sand casting, the RE Mg alloys prepared by the squeezecasting were provided with the finest grain size, the best mechanical properties andcorrosion-resistant performance.
The investigation to the compressive stress-strain behavior of two kinds of theRE Mg alloys showed that the RE Mg alloys belong to the materials being sensive topositive strain rate, and the hot-compression plastic deformation of the RE Mg alloyswas up to the thermal activation.
The investigation to the Mg-Nd-Gd-Zn-Zr alloy shows that, the RE Mg alloyswith favorable corrosion-resistant performance and casting processing performancecould be achieved by composition design and optimization, and the prepared alloy canbe provided with comprehensive properties by reasonable heat treatment. Because oflow-content RE, the precipitate strengthening effect of aging for the extruded alloywas not predominant, and the interaction between the dislocations and the RE secondphases was not obvious.
The microstructures of the high RE-content as-cast Mg-xGd-3Y-Zn-0.5Zr alloys were consists of α-Mg and βphases（Mg_5Gd(Y,Zn)）, and with the increase of the Gdcontent, the grain size of the alloys became finer and the eutectic phases on the grainboundaries transformed from continuous network-shape distribution to discontinuousdispersion distribution and the volume fraction of eutectic phases were also increasedcorrespondingly. During solution treatment, theβphases at the grain boundariesdescomposed and transferred into the block-shaped and lamellar-shaped14H-LPSOstructure phases. These LSPO structure phases were composed of elements of Mg, Zn,Gd and Y, and Zn was the key element for the formation of14H-LPSO structurephases. With the solution time further prolonged, the block-shaped phases alsogradually transferred into lamellar-shaped14H-LPSO structure phases. With the Gdcontent added, the peak hardness increased and the time to reach the peak hardnesswas shortened. With the temperature raised, the peak hardness decreased and the timeto reach the peak hardness was shortened. For Mg-8Gd-3Y-Zn-0.5Zr alloy, the β'phases precipitated and dispersed at200℃aging temperature, but β' phases were notobserved when aging at250℃. For Mg-12Gd-3Y-Zn-0.5Zr alloy, the size of β' phaseswas increased and the quantitiy of β' phases was reduced when aging temperature wasraised, the distributed high-density β' phases were contributed to aging hardeningeffects at200℃and225℃. When aging at250℃, the precipitated phases of theMg-12Gd-3Y-Zn-0.5Zr alloy were composed of β' phases and β1phases, and the β'phases were gradually transformed into β1phases with the aging time prolonged.
The investigation to the mechanical properties of cast Mg-xGd-3Y-Zn-0.5Zralloys shows that, when Gd content is not below10wt%, the ultimate tensile strengthincreased with the temperature raised between room temperatue and200℃, andreached peak value near200℃and then dropped gradually. At room temperature, thefracture mode of Mg-xGd-3Y-Zn-0.5Zr alloys was cleavage fracture and the plasticityof the alloys was dropped with the increase of Gd content. The fracture mode of thealloys was quasi-cleavage crack at elevated temperature.
The grain size of the Mg-xGd-3Y-Zn-0.5Zr was obviously refined after hotextrusion and the aging strengthening effect of the extruded alloys was predominant.The peak values of the mechanical properties were492MPa (ultimate tensile strength)and11%(elongation rate). They were endued with favorable plasticity.
通过研究稀土元素对镁合金耐蚀性的影响机制发现：添加稀土元素后形成的第二相与镁基体的镁合金的电极电位差变小，导致微电偶腐蚀的驱动力相应减弱，微电偶腐蚀的极化电流变小，腐蚀速率降低；稀土元素可以通过改变金属表面氧化膜的结构提高致密度、细化晶粒、改变了镁合金中第二相的组成、形态和分布等，从而改善了镁合金耐腐蚀性。
稀土镁合金材料制备工艺过程中，保持成分均匀稳定、减少熔剂夹杂和熔体吹洗等途径有利于合金耐蚀性的改善；挤压铸造、金属型铸造和砂型铸造三种方法相比，挤压铸造制备的合金组织晶粒更细、力学性能和耐蚀性更好。
对两类不同稀土含量的镁合金的压缩应力应变行为的研究表明二者均是正应变速率敏感材料，合金热压缩塑性变形是受热激活控制的。
对Mg-Nd-Gd-Zn-Zr合金的研究表明，通过成分设计可以实现低稀土含量的镁合金具有良好的耐蚀性，铸态合金通过合理的热处理工艺可以实现强度和伸长率的综合优化；由于稀土含量不高，挤压变形后的合金经时效处理时析出强化效果有限，位错与稀土第二相的交互作用不明显。
高稀土含量的Mg-xGd-3Y-Zn-0.5Zr合金的铸态组织由α-Mg和β相（Mg_5Gd(Y,Zn)）组成，且随着Gd含量的增加，晶粒尺寸呈细化趋势，晶界共晶相由连续网状分布转变为断续状弥散分布，且共晶相数量也相应增加。合金经固溶处理后，合金晶界β相（Mg_5Gd(Y,Zn)分解并生成成分有序和堆垛有序的块状、层片状的14H-LPSO结构相，这些LPSO相是由Mg、Zn、Gd和Y元素组成，而Zn是形成14H-LPSO的关键合金元素。合金时效峰值硬度随Gd含量的增加而增高，到达峰值硬度的时间随Gd含量的增加而缩短；随温度升高，峰值硬度降低，到达峰值硬度的时间缩短。8%wtGd的合金200℃时效析出弥散分布的β'相，而250℃时效未发现明显的弥散析出相。12wt%Gd的合金随时效温度的升高，峰值硬化组织时效析出β'相尺寸增大，数量减少；在200℃和225℃的时效硬化归因为高致密分布的β'相；在250℃的峰值硬化组织析出相是β'相和β1，后随时间延长β'相逐渐向β1转变。
对铸造Mg-xGd-3Y-Zn-0.5Zr合金的力学性能研究发现，常温抗拉强度接近，伸长率对Gd含量增加而降低。Gd含量不低于10wt%的合金的抗拉强度在室温~200℃呈增加趋势并在200℃附近达到最大，随后逐渐下降。对合金失效断口分析发现，合金在室温的断裂主要是解理断裂且随Gd含量的增加脆性增加，高温断裂表现为准解理断裂。
Mg-xGd-3Y-Zn-0.5Zr合金经过挤压变形后晶粒显著细化，挤压合金时效强化效应显著，合金力学性能最高时强度和伸长率分别为492MPa和11%，具有良好的塑韧性。
To meet the demand of corrosion-resistant and high-strength magnesium alloy,this paper was engaged in the study of the effects and influence mechanisms of Rareearth (RE) to the corrosion-resistant performance and mechanical properties. Twokinds of alloys with different RE contents were involved to study the influence ofcasting, heat treatment and hot-extrusion deformation processes to the microstructuresand properties of the alloys.
By investigating the influence mechanism of RE elements to thecorrosion-resistant performance of Mg alloy, it shows that, the voltage between theMg matrix and the RE second phases is decreased and the driving force of microelectrical-couple corrosion became weak and corrosion rate was dropped; thecorrosion-resistant performance was improved by the RE elements through the meansof optimizing the structure of the oxidation film to increase the film density, refiningthe grain size, changing the composition, shape and distribution of the second phases.
The approaches of guaranting the stability of the RE Mg alloy, reducing the fluximpurities and gas purifying the melt were helpful to improve the corrosion-resistantperformance of the RE Mg alloy. Among the three methods of the squeeze casting,metal mold casting and sand casting, the RE Mg alloys prepared by the squeezecasting were provided with the finest grain size, the best mechanical properties andcorrosion-resistant performance.
The investigation to the compressive stress-strain behavior of two kinds of theRE Mg alloys showed that the RE Mg alloys belong to the materials being sensive topositive strain rate, and the hot-compression plastic deformation of the RE Mg alloyswas up to the thermal activation.
The investigation to the Mg-Nd-Gd-Zn-Zr alloy shows that, the RE Mg alloyswith favorable corrosion-resistant performance and casting processing performancecould be achieved by composition design and optimization, and the prepared alloy canbe provided with comprehensive properties by reasonable heat treatment. Because oflow-content RE, the precipitate strengthening effect of aging for the extruded alloywas not predominant, and the interaction between the dislocations and the RE secondphases was not obvious.
The microstructures of the high RE-content as-cast Mg-xGd-3Y-Zn-0.5Zr alloys were consists of α-Mg and βphases（Mg_5Gd(Y,Zn)）, and with the increase of the Gdcontent, the grain size of the alloys became finer and the eutectic phases on the grainboundaries transformed from continuous network-shape distribution to discontinuousdispersion distribution and the volume fraction of eutectic phases were also increasedcorrespondingly. During solution treatment, theβphases at the grain boundariesdescomposed and transferred into the block-shaped and lamellar-shaped14H-LPSOstructure phases. These LSPO structure phases were composed of elements of Mg, Zn,Gd and Y, and Zn was the key element for the formation of14H-LPSO structurephases. With the solution time further prolonged, the block-shaped phases alsogradually transferred into lamellar-shaped14H-LPSO structure phases. With the Gdcontent added, the peak hardness increased and the time to reach the peak hardnesswas shortened. With the temperature raised, the peak hardness decreased and the timeto reach the peak hardness was shortened. For Mg-8Gd-3Y-Zn-0.5Zr alloy, the β'phases precipitated and dispersed at200℃aging temperature, but β' phases were notobserved when aging at250℃. For Mg-12Gd-3Y-Zn-0.5Zr alloy, the size of β' phaseswas increased and the quantitiy of β' phases was reduced when aging temperature wasraised, the distributed high-density β' phases were contributed to aging hardeningeffects at200℃and225℃. When aging at250℃, the precipitated phases of theMg-12Gd-3Y-Zn-0.5Zr alloy were composed of β' phases and β1phases, and the β'phases were gradually transformed into β1phases with the aging time prolonged.
The investigation to the mechanical properties of cast Mg-xGd-3Y-Zn-0.5Zralloys shows that, when Gd content is not below10wt%, the ultimate tensile strengthincreased with the temperature raised between room temperatue and200℃, andreached peak value near200℃and then dropped gradually. At room temperature, thefracture mode of Mg-xGd-3Y-Zn-0.5Zr alloys was cleavage fracture and the plasticityof the alloys was dropped with the increase of Gd content. The fracture mode of thealloys was quasi-cleavage crack at elevated temperature.
The grain size of the Mg-xGd-3Y-Zn-0.5Zr was obviously refined after hotextrusion and the aging strengthening effect of the extruded alloys was predominant.The peak values of the mechanical properties were492MPa (ultimate tensile strength)and11%(elongation rate). They were endued with favorable plasticity.
引文
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