镁基非晶复合材料微观结构与力学性能
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摘要
普通镁合金作为最轻的结构材料，已经在汽车、电子、航空等领域得到应用，然而，镁合金强度低，耐蚀性差，应用范围受到了限制。镁基非晶合金虽然强度和耐蚀性得到了改善，但脆性大。相比之下，镁基非晶复合材料则具有更好的综合力学性能，是这一领域的研究热点。
本文以具有大非晶形成能力的Mg-Cu-Y合金为基础，通过添加Be、Ti、Zr等合金元素，研究了非晶复合材料的微观结构与力学性能的关系，合金元素添加与相分离的关系以及双相非晶的形成机制。此外，以具有长周期结构的Mg-Ni-Zn-Y非晶复合材料为基础，对其相组成、空间结构和断裂机制进行了系统研究。获得了以下结果：
采用铜模铸造法制备出直径为3mm的(Mg0.585Cu0.305Y0.11)100-xBex(x=3，5，7，10)系列合金。该系列合金由于Be的加入而产生了Cu-Y-Be第二相，其尺寸和数量随着Be元素加入量的增加而增加。合金的压缩断裂强度分别为866、954、1086和953MPa，呈现出先增加后降低的趋势。通过对(Mg0.585Cu0.305Y0.11)95Be5合金进行TEM和选区衍射分析可知合金产生了相分离，合金中的第二相由Cu-Y-Be非晶相和CuY晶态相组成。直径为1、2和3mm的(Mg0.585Cu0.305Y0.11)95Be5合金试样的压缩断裂强度分别为959、955和954MPa，表明该合金的压缩断裂强度具有尺寸相对独立性。
研究了(Mg0.585Cu0.305Y0.11)90Ti10和(Mg0.585Cu0.305Y0.11)90(Ti0.7Be0.3)10合金。在两种合金中都分布着大量的白色CuTi晶态点状相。后者中第二相的尺寸更大，数量更多，且其中包含一定的非晶相。直径为3mm的两种合金的压缩断裂强度分别为798和1008MPa，比Mg58.5Cu30.5Y11合金的压缩断裂强度分别提高了17%和48%。(Mg0.585Cu0.305Y0.11)90Ti10和(Mg0.585Cu0.305Y0.11)90(Ti0.7Be0.3)10两种合金的最大强度和最小强度的比值分别为5.1%和4.8%，而Mg58.5Cu30.5Y11合金的比值则为15.5%，表明Ti和Ti70Be30的加入提高了Mg基块体非晶合金的强度可靠性。
研究了直径为3mm的(Mg0.585Cu0.305Y0.11)97(Zr0.35Ti0.3Be0.275Cu0.075)3合金的微观结构和力学性能。通过SEM可以观察到在该合金富Mg非晶基体之中分布着富Zr的球状非晶第二相。TEM和选区衍射分析表明合金在凝固过程中产生了相分离，形成了富Mg和富Zr的双相非晶。该合金的压缩断裂强度、弹性变形量和塑性变形量分别为1026MPa、2.2%和0.3%，表明合金的力学性能因为发生了相分离而有了很大提高。相分离产生的富Zr硬相在合金的压缩过程中能阻碍剪切带的扩展，进而促使新剪切带萌生，使剪切带增殖并发生交互作用，从而提高了合金的压缩断裂强度并使合金产生了塑性变形。
研究了直径为2mm的含有长周期相的Mg81Ni8Zn5Y6非晶合金复合材料。该合金由富Mg非晶基体相、Mg12ZnY晶态相、α-Mg相和一种菱形立方结构的四元亚稳白色点状相组成，其中Mg12ZnY为14H型长周期相，在合金中具有空间网状结构。合金的断裂强度、屈服强度和塑性变形量分别为678MPa、510MPa和12.9%。合金的断裂过程可以分为应力集中阶段、剪切带形成的胚胎阶段、完整的剪切带形成阶段、剪切带的传播阶段、剪切带的增殖阶段以及合金的断裂等六个阶段。
As the lightest structural material, the ordinary Mg alloy has been applied in automobileindustry, electronics, aerospace industry and other fields. However, the application scope ofMg alloy is limited due to its low strength and poor corrosion resistance. For Mg-based bulkmetallic glasses (BMGs), the strength and corrosion resistance have been improved, but theyare brittle. The Mg-based BMG matrix composites, by contrast, have better comprehensivemechanical properties, which are the research hotspot in this field.
Based on the Mg-Cu-Y alloy with high glass forming ability, the relationship betweenmicrostructure and mechanical properties for BMG matrix composite, the relationship betweenalloying element addition and phase separation, the formation mechanism of two-phaseglasses were investigated by adding Be, Ti and Zr alloying elements into the alloy. In addition,based on the Mg-Ni-Zn-Y BMG matrix composite with long period stacking order (LPSO)structure, the phase composition, spatial structure and fracture mechanism of the alloy weresystematically researched. The main experimental results are as following:
The (Mg0.585Cu0.305Y0.11)100-xBex(x=3,5,7,10) alloys with3mm in diameter werefabricated by conventional Cu-mould casting method. The Cu-Y-Be second phase isdistributed in the alloys because of Be addition. The size and the quantity of the second phaseare increased with the increase of Be content. The compressive fracture strengths of the alloysare866,954,1086and953MPa, respectively, presenting a trend of first increase and thendecrease. It is known by using TEM and selected area electron diffraction analyses that phaseseparation was occurred in (Mg0.585Cu0.305Y0.11)95Be5alloy. The second phase of the alloy isconsisted of Cu-Y-Be amorphous phase and CuY crystalline phase. The compressive fracturestrengths of the samples with1,2and3mm in diameters for (Mg0.585Cu0.305Y0.11)95Be5alloyare959,955and954MPa, respectively, indicating the sample-size independence ofcompressive fracture strength.
The (Mg0.585Cu0.305Y0.11)90Ti10and (Mg0.585Cu0.305Y0.11)90(Ti0.7Be0.3)10alloys wereinvestigated. A number of white CuTi crystalline phases are distributed in these two alloys.The second phase in the latter, which contain some amorphous phase, is bigger and more thanthat in the former. The compressive fracture strengths of these two alloys with3mm in diameter are798and1008MPa, respectively, which are increased by about17%and48%than that of Mg58.5Cu30.5Y11alloy. Compared with15.5%strength ratio between the maximumand the minimum fracture strength values for Mg58.5Cu30.5Y11alloy, the values5.1%and4.8%for the (Mg0.585Cu0.305Y0.11)90Ti10and (Mg0.585Cu0.305Y0.11)90(Ti0.7Be0.3)10alloys indicate thattheir strength reliability is improved by Ti and Ti70Be30addition.
The microstructure and mechanical properties for the(Mg0.585Cu0.305Y0.11)97(Zr0.35Ti0.3Be0.275Cu0.075)3alloy with3mm in diameter were investigated.The Zr-rich amorphous spherical phase distributed in the Mg-rich glassy matrix was observedby using SEM. Based on the TEM and selected area electron diffraction analyses, it isindicated that the phase separation was occurred in the alloy during the solidification process,forming the Mg-rich and Zr-rich two-phase glasses. The compressive fracture strength, elasticstrain and plastic strain of the alloy are1026MPa,2.2%and0.3%, respectively, indicating theimprovement of the mechanical properties for the alloy. The improvement of compressivefracture strength and the formation of plastic deformation for the BMG are attributed to theshear-band propagation, multiplication and interaction caused by the hard Zr-rich amorphousspherical phase.
The Mg81Ni8Zn5Y6BMG matrix composite containing LPSO phase with2mm indiameter was investigated. The alloy is consisted of Mg-rich amorphous matrix phase,Mg12ZnY crystalline phase, α-Mg phase and a diamond-cubic quaternary metastable phase.The Mg12ZnY is a14H-type LPSO phase, which is distributed in the glass matrix as net-liketexture. The fracture strength, yield strength and plastic strain of the alloy are678MPa,510MPa and12.9%, respectively. Six stages of fracture process for the alloy can be outlined asstress concentration, embryonic shear bands formation, mature shear bands formation, shearbands propagation, shear band multiplication and shear-off.
本文以具有大非晶形成能力的Mg-Cu-Y合金为基础，通过添加Be、Ti、Zr等合金元素，研究了非晶复合材料的微观结构与力学性能的关系，合金元素添加与相分离的关系以及双相非晶的形成机制。此外，以具有长周期结构的Mg-Ni-Zn-Y非晶复合材料为基础，对其相组成、空间结构和断裂机制进行了系统研究。获得了以下结果：
采用铜模铸造法制备出直径为3mm的(Mg0.585Cu0.305Y0.11)100-xBex(x=3，5，7，10)系列合金。该系列合金由于Be的加入而产生了Cu-Y-Be第二相，其尺寸和数量随着Be元素加入量的增加而增加。合金的压缩断裂强度分别为866、954、1086和953MPa，呈现出先增加后降低的趋势。通过对(Mg0.585Cu0.305Y0.11)95Be5合金进行TEM和选区衍射分析可知合金产生了相分离，合金中的第二相由Cu-Y-Be非晶相和CuY晶态相组成。直径为1、2和3mm的(Mg0.585Cu0.305Y0.11)95Be5合金试样的压缩断裂强度分别为959、955和954MPa，表明该合金的压缩断裂强度具有尺寸相对独立性。
研究了(Mg0.585Cu0.305Y0.11)90Ti10和(Mg0.585Cu0.305Y0.11)90(Ti0.7Be0.3)10合金。在两种合金中都分布着大量的白色CuTi晶态点状相。后者中第二相的尺寸更大，数量更多，且其中包含一定的非晶相。直径为3mm的两种合金的压缩断裂强度分别为798和1008MPa，比Mg58.5Cu30.5Y11合金的压缩断裂强度分别提高了17%和48%。(Mg0.585Cu0.305Y0.11)90Ti10和(Mg0.585Cu0.305Y0.11)90(Ti0.7Be0.3)10两种合金的最大强度和最小强度的比值分别为5.1%和4.8%，而Mg58.5Cu30.5Y11合金的比值则为15.5%，表明Ti和Ti70Be30的加入提高了Mg基块体非晶合金的强度可靠性。
研究了直径为3mm的(Mg0.585Cu0.305Y0.11)97(Zr0.35Ti0.3Be0.275Cu0.075)3合金的微观结构和力学性能。通过SEM可以观察到在该合金富Mg非晶基体之中分布着富Zr的球状非晶第二相。TEM和选区衍射分析表明合金在凝固过程中产生了相分离，形成了富Mg和富Zr的双相非晶。该合金的压缩断裂强度、弹性变形量和塑性变形量分别为1026MPa、2.2%和0.3%，表明合金的力学性能因为发生了相分离而有了很大提高。相分离产生的富Zr硬相在合金的压缩过程中能阻碍剪切带的扩展，进而促使新剪切带萌生，使剪切带增殖并发生交互作用，从而提高了合金的压缩断裂强度并使合金产生了塑性变形。
研究了直径为2mm的含有长周期相的Mg81Ni8Zn5Y6非晶合金复合材料。该合金由富Mg非晶基体相、Mg12ZnY晶态相、α-Mg相和一种菱形立方结构的四元亚稳白色点状相组成，其中Mg12ZnY为14H型长周期相，在合金中具有空间网状结构。合金的断裂强度、屈服强度和塑性变形量分别为678MPa、510MPa和12.9%。合金的断裂过程可以分为应力集中阶段、剪切带形成的胚胎阶段、完整的剪切带形成阶段、剪切带的传播阶段、剪切带的增殖阶段以及合金的断裂等六个阶段。
As the lightest structural material, the ordinary Mg alloy has been applied in automobileindustry, electronics, aerospace industry and other fields. However, the application scope ofMg alloy is limited due to its low strength and poor corrosion resistance. For Mg-based bulkmetallic glasses (BMGs), the strength and corrosion resistance have been improved, but theyare brittle. The Mg-based BMG matrix composites, by contrast, have better comprehensivemechanical properties, which are the research hotspot in this field.
Based on the Mg-Cu-Y alloy with high glass forming ability, the relationship betweenmicrostructure and mechanical properties for BMG matrix composite, the relationship betweenalloying element addition and phase separation, the formation mechanism of two-phaseglasses were investigated by adding Be, Ti and Zr alloying elements into the alloy. In addition,based on the Mg-Ni-Zn-Y BMG matrix composite with long period stacking order (LPSO)structure, the phase composition, spatial structure and fracture mechanism of the alloy weresystematically researched. The main experimental results are as following:
The (Mg0.585Cu0.305Y0.11)100-xBex(x=3,5,7,10) alloys with3mm in diameter werefabricated by conventional Cu-mould casting method. The Cu-Y-Be second phase isdistributed in the alloys because of Be addition. The size and the quantity of the second phaseare increased with the increase of Be content. The compressive fracture strengths of the alloysare866,954,1086and953MPa, respectively, presenting a trend of first increase and thendecrease. It is known by using TEM and selected area electron diffraction analyses that phaseseparation was occurred in (Mg0.585Cu0.305Y0.11)95Be5alloy. The second phase of the alloy isconsisted of Cu-Y-Be amorphous phase and CuY crystalline phase. The compressive fracturestrengths of the samples with1,2and3mm in diameters for (Mg0.585Cu0.305Y0.11)95Be5alloyare959,955and954MPa, respectively, indicating the sample-size independence ofcompressive fracture strength.
The (Mg0.585Cu0.305Y0.11)90Ti10and (Mg0.585Cu0.305Y0.11)90(Ti0.7Be0.3)10alloys wereinvestigated. A number of white CuTi crystalline phases are distributed in these two alloys.The second phase in the latter, which contain some amorphous phase, is bigger and more thanthat in the former. The compressive fracture strengths of these two alloys with3mm in diameter are798and1008MPa, respectively, which are increased by about17%and48%than that of Mg58.5Cu30.5Y11alloy. Compared with15.5%strength ratio between the maximumand the minimum fracture strength values for Mg58.5Cu30.5Y11alloy, the values5.1%and4.8%for the (Mg0.585Cu0.305Y0.11)90Ti10and (Mg0.585Cu0.305Y0.11)90(Ti0.7Be0.3)10alloys indicate thattheir strength reliability is improved by Ti and Ti70Be30addition.
The microstructure and mechanical properties for the(Mg0.585Cu0.305Y0.11)97(Zr0.35Ti0.3Be0.275Cu0.075)3alloy with3mm in diameter were investigated.The Zr-rich amorphous spherical phase distributed in the Mg-rich glassy matrix was observedby using SEM. Based on the TEM and selected area electron diffraction analyses, it isindicated that the phase separation was occurred in the alloy during the solidification process,forming the Mg-rich and Zr-rich two-phase glasses. The compressive fracture strength, elasticstrain and plastic strain of the alloy are1026MPa,2.2%and0.3%, respectively, indicating theimprovement of the mechanical properties for the alloy. The improvement of compressivefracture strength and the formation of plastic deformation for the BMG are attributed to theshear-band propagation, multiplication and interaction caused by the hard Zr-rich amorphousspherical phase.
The Mg81Ni8Zn5Y6BMG matrix composite containing LPSO phase with2mm indiameter was investigated. The alloy is consisted of Mg-rich amorphous matrix phase,Mg12ZnY crystalline phase, α-Mg phase and a diamond-cubic quaternary metastable phase.The Mg12ZnY is a14H-type LPSO phase, which is distributed in the glass matrix as net-liketexture. The fracture strength, yield strength and plastic strain of the alloy are678MPa,510MPa and12.9%, respectively. Six stages of fracture process for the alloy can be outlined asstress concentration, embryonic shear bands formation, mature shear bands formation, shearbands propagation, shear band multiplication and shear-off.
引文
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